Thionyl Chloride → HCID 22493765, compound

HRID 916877Notes

Reaction equation

HRID 916877 reaction equation
[CH2:1]([N:5]1[C:9]([CH2:10]O)=[CH:8][N:7]=[C:6]1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:2][CH2:3][CH3:4].S(Cl)(Cl)=O.[CH2:22]([NH2:32])[C:23]1[CH:31]=[CH:30][C:29]2[O:28][CH2:27][O:26][C:25]=2[CH:24]=1>C(Cl)(Cl)Cl.C(#N)C>[CH2:1]([N:5]1[C:9]([CH2:10][NH:32][CH2:22][C:23]2[CH:31]=[CH:30][C:29]3[O:28][CH2:27][O:26][C:25]=3[CH:24]=2)=[CH:8][N:7]=[C:6]1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:2][CH2:3][CH3:4]

Participants

6

Reactant 3

HCID 24386Thionyl ChlorideHCID 75799Benzo-1,3-dioxole-5-methylamineHCID 22493824HCID 22493824, compound

Product 1

HCID 22493765HCID 22493765, compound

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6342AcetonitrileSolvent2×

Conditions

Temperature
50 °C

Procedure

Hydroxymethylimidazole 103 (0.82 g) is dissolved in chloroform (10 ml) and treated with thionyl chloride (1 ml). The solution is heated to 50° C. for 30 min, cooled and evaporated. The residue is washed with benzene and evaporated to give the intermediate chloromethyl hydrochloride as a white powder which is taken up in acetonitrile (30 mL). This is added dropwise to a solution of piperonylamine (5 ml) in acetonitrile (10 mL). The reaction is allowed to stand overnight and then evaporated. The residue is taken up in ethyl acetate and washed with water. The organic layer is dried (Na2SO4) and concentrated. Purification on silica gel (10% MeOH/CHCl3) provides the product as a pale yellow oil (0.91 g). 1H NMR (400 MHz, CDCl3): δ 0.79 (3H, t, d=7.4), 1.18 (2H, m, d=7.4), 1.56 (2H, m, d=7.4), 3.75 (4H, s), 4.04 (2H, dd, d=8), 5.92 (2H, s), 6.76 (2H, m), 6.84 (1H,s), 6.97 (1H, s), 7.38–7.44 (3H, m), 7.53–7.56 (2H, m).

Workup

  1. temperaturecooled
  2. customevaporated
  3. washThe residue is washed with benzene
  4. customevaporated
  5. customto give the intermediate chloromethyl hydrochloride as a white powder which
  6. customevaporated
  7. washwashed with water
  8. dry with materialThe organic layer is dried (Na2SO4)
  9. concentrationconcentrated
  10. customPurification on silica gel (10% MeOH/CHCl3)

Sources & evidence

ORD record
ord-ccf6bb602e7c4cb391ede78d556f5d05
Source dataset
uspto-grants-2007_09
Patent number
US07271270B2

Reaction notes

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